Bio-based device for temperature-controlled systems

Abstract

Devices for use in thermally controlled package systems that include body of open cell, low-density, rigid, bio-based polymeric foam material and a phase change material (PCM) absorbed therein, which are enclosed within a leakproof container preferably formed of polymeric film. Additives can be present in the foam body and / or the PCM. The foam body is preferably formed of one or a combination of tannin resins, lignin resins, cardanol resins, furfuryl alcohol resins, and bio-based phenol resins, has a 90 to 99% open cell content, a density of 1.0 to 2.0 lb / ft3, a compression strength of 6.0 to 18 lbf / in2, macropores with a diameter of 50 to 500 microns, and micropores with a diameter of 0.5 to 50 microns. Suitable PCMs include water, paraffin waxes, water-salt eutectic solutions, water-eutectic solutions, salt hydrates, fatty acids, alkyl esters of fatty acids, fatty alcohols, fatty sulfonates or phosphonates and combinations thereof.

Description

BIO-BASED DEVICE FOR TEMPERATURE-CONTROLLED SYSTEMSPRIORITY CLAIM

[0001] This International Application claims priority to U.S. Provisional Pat. App. Ser. No. 63 / 749,509, filed January 25, 2025.BACKGROUND OF INVENTION

[0002] Field of Invention

[0003] The present disclosure relates to devices for thermally controlled package systems and methods for making and using the same. Devices according to the invention include a phase change material ("PCM") and optional additives absorbed into a body of open cell, low density, rigid, bio-based polymeric foam material, both of which being sealed within a container preferably made of a polymer film.

[0004] Brief Description of Related Art

[0005] A PCM is a substance that releases / absorbs energy through a phase transition to provide useful heat / cooling. Generally, the transition will be from one of the first two fundamental states of matter (solid and liquid) to the other. Latent heat storage using PCMs is one of the most efficient methods to store / release thermal energy. See Oro, E., De Gracia, A., Castell, A., Farid, M.M. and Cabeza, L.F., 2012. Review on phase change materials (PCMs) for cold thermal energy storage applications. Applied Energy, 99, pp.513-533.

[0006] PCMs that have high energy storage density and high-power capacity for charging and discharging are desirable properties of any energy storage system. Storage energy systems have been studied to address problems such as domestic hot water, cooling and heating of buildings, solar energy applications, and, more recently, cold thermal energy systems for various applications such as food storage, transport of temperature-sensitive materials, and air conditioning.

[0007] T ransport containers for temperature-sensitive materials is one of the most known applications of PCMs. These containers must be kept at low temperatures before use to solidify the PCM. Most widely spread are plastic bottles that have a PCM with melting points of 0 °C, 5 °C, and -21 °C. Another example is the use of PCM pads for use in any carrier container. Other PCM composites with different latent heats in the -50 to 30 °C range for chilled, cold, and room temperature storage packaging have been developed as well.

[0008] Research and application of PCMs to transport temperature-sensitive materials has been advancing at a great pace for the last 20 years. U.S. Pat. No. 8,443,623 discloses a device and how to make a phase change device for controlling the temperature in enclosed environments, used for controlling packages for shipment or transport. An open-cell phenolic-base foam with a phase change absorbed inside of the foam is used.

[0009] U.S. Pat. No. 6,765,031 discloses a microporous open cell foam composite and a method for manufacturing a micropore open cell foam composite wherein the micropore open cell foam composites comprise a micropore open cell foam having an open cell content of greater than about 80% volume and an average pore size of about 200 microns or less and a phase change material in the open cell foam in the amount of 80% volume or greater.

[0010] Open-cell phenolic foams are well-known. Smithers, U.S. Pat. No.2,753,277, discloses an open-cell phenolic foam for the insertion of cut flower stems for floral arrangements or plant cuttings for rooting and propagating of garden and house plants. Phenolic open-cell polymeric foam commercially available for this purpose can absorb liquids, including phase change materials. Foams of this type typically have an apparent density of 0.017 - 0.028 g / cm3, with a typical compression strength of 10 - 30 lbf / in2.

[0011] Bio-based phenolic foams based on tannin and furfuryl alcohol have been cited in the literature and in the disclosures of various patents including Cobb et al., U.S. Pat No. 9,260,579 B2, Pizzi et al., U.S. Pat. No. 9,302,413 B2, Cobb et al., U.S. Pat. No. 9,701,803 B2, Harmer et al., U.S. Pat. No. 9,790,342 B2 and Clezard et al., U.S. Pat. No. 9,994,690 B2. Most of the foams described in the scientific and patent literature are substantially closed-cell foams. A bio-based open cell phenolic floral foam based on tannin, glutaraldehyde and furfuryl alcohol is described in Basso, M.C. et al., Horticultural / hydroponics and floral natural foams from tannin, Industrial Crops and Products 87 (2016) 177-181. In practice, these foams tend to be difficult to commercially produce in larger sizes due to the higher foaming reactivity, resulting in non-uniform foam and voiding.BRIEF SUMMARY OF THE INVENTION

[0012] The present invention relates to the use of an open cell, low density, rigid, bio-based polymeric foam material comprised of one or more materials consisting oftannin resins, lignin resins, cardanol resins, furfuryl alcohol resins, and bio-based phenol resins, which has a phase change material absorbed inside its open cells, in leakproof thermally controlled package systems.

[0013] The foregoing and other features of the invention are hereinafter more fully described below, the following description setting forth in detail certain illustrative embodiments of the invention, these being indicative, however, of but a few of the various ways in which the principles of the present invention may be employed.BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Fig. 1 is a perspective view of a body of open-cell, low density, rigid, biobased polymeric foam material.

[0015] Fig. 2 is a close-up view of an identified area of the foam material shown in Fig. 1.

[0016] Fig. 3 is a top plan view of an exemplary device for use in a thermally controlled package system according to the invention.

[0017] Fig. 4 is a section view of the exemplary device shown in Fig. 3 taken along the lines 4-4, which shows a body of open-cell, low density, rigid, bio-based polymeric foam material as shown in Fig. 1 that has absorbed a phase change material and is enclosed within a leakproof container.

[0018] Fig. 5 is a top view of an exemplary shipping container before it has been filled with a temperature-controlled product and sealed, which includes a paperboard box, insulation and a device as shown in Fig. 3

[0019] Fig. 6 is a section view of the shipping container according to Fig. 5 taken along the lines 6-6 after it has been filled with a temperature-controlled product and sealed, showing the insulation and devices as shown in Fig. 2 contained therein.

[0020] Fig. 7 is a graph showing room temperature (RT) and the inside temperature measured at the top of a payload box contained within a shipping container as shown in Fig. 5 as a function of time according to Example 5.

[0021] Fig. 8 is a graph showing room temperature (RT) and the inside temperature measured at the top of a payload box contained within a shipping container as shown in Fig. 5 as a function of time according to Example 6.DETAILED DESCRIPTION OF THE INVENTION

[0022] The present disclosure relates to devices for thermally controlled package systems and methods for making and using the same. A device preferably comprises a body formed of an open cell, low density, rigid (i.e. , non-flexible), biobased polymeric foam material and a PCM and optional additives absorbed in the open cells of the body of foam material, wherein the body of foam material is shapestable upon absorption of the PCM. Both the body of foam material and the PCM absorbed therein are enclosed within a leakproof container preferably formed of polymeric film. The optional additives can be dissolved in the PCM that is absorbed into the open cells of the body of foam material and / or can be present in the body of foam material before the PCM is absorbed therein. The disclosed device exhibits properties that make it particularly useful in thermally controlled package systems.

[0023] The body is preferably a bio-based open-cell foam material. Throughout the instant specification and in the appended claims, the term "bio-based" denotes that the foam material predominantly comprises polymers that are of plant origin as opposed to synthetic and / or petroleum derived polymers. The term "predominantly" means at least 50% by weight, and more preferably at least 70% by weight. In the most preferred embodiment, the bio-based open cell foam material has a 4-star biobased content according to TUV Austria’s review and certification criteria (i.e., a biobased content greater than 80% by weight).

[0024] The bio-based open cell foam material can be formed from one or a blend of two or more selected from the group consisting of tannin resins, lignin resins, cardanol resins, furfuryl alcohol resins, and bio-based phenol resins. Alternatively, the body can be formed of polyurethane foam made from bio-based polyols such as soybean oil, castor oil, palm oil, cardanol, glycerol, and other hydroxyl-containing plant-based materials, starch foams, polylactic acid foams (PLA), polyhydroxyalkanoate foams, cellulose foams, cellulose acetate foams, cellulose ester foams, cellulose fiber-based foams (wood fiber, cellulose nanofiber (CNF)), microfibrillated cellulose (MFC), lignocellulosic foams, chitin and chitosan based foams, bio-based polybutylene succinate (PBS) foams, alginate based foams, and cellulose acetate foams. The body of foam material can include further components such as surfactants, blowing agents, and catalysts. Bio-based polymeric foams suitable for use in the invention are preferably dimensionally stable under compressive load, tend to be susceptible to catastrophic fracture without plasticdeformation (i.e., brittle), and prone to produce mass loss (i.e., powder or small fragments) detachment under standard handling conditions (i.e., friable). These foams have a strong tendency towards open cells. Open-cell foam has interconnected, ruptured cells, creating a sponge-like structure that can absorb liquid. Due to the open cell nature and hydroxyl groups along the polymeric chains, these foams will readily absorb liquids, and due to their unique structure, they retain liquids in the cells.

[0025] Bio-based open cell foam materials suitable for use in the invention preferably exhibit a density within the range from 1.0 to 2.0 lb / ft3(0.017 - 0.032 g / cm3), preferably exhibit a compression strength of 6.0 to 18 lbf / in2, preferably exhibit an open cell content of about 70% to about 99% (most preferably > 90%) and an average water uptake around 98 w / v%. The PCM saturation range for the body of foam material is preferably 50 to 95% w / v, or more preferably 80 to 95% w / v of the dimensions of the body of foam material. Bio-based open cell foams materials suitable for use in the invention are shape-stable for absorbing the PCM, and preferably exhibit macropores having a diameter of about 50 to about 500 microns, and micropores having a diameter between about 0.5 and about 50 microns. A biobased foam material of the type described as being suitable for use herein is commercially available from Smithers-Oasis Company under the OASIS® Renewal® Floral Foam trade designation.

[0026] Fig. 1 is a perspective view of an exemplary body of open-cell, low density, rigid (i.e., non-flexible), bio-based polymeric foam material 10. In the illustrated embodiment, the body of foam material 10 has a rectangular shape with a top side 20, a bottom side 30, opposed left and right sides 40, 50, and opposed front and rear sides 60, 70. Fig. 2 is a close-up view of the area 80 of the front side 60 of the body of foam material 10 enclosed within the circle on Fig. 1. As shown in Fig.2, the body of foam material 10 includes interconnected, ruptured cells 90 that are capable of absorbing a liquid phase change material. It will be appreciated that the body of foam material can have any desired shape and that a rectangular block is shown for illustrative purposes only.

[0027] The bio-foam material and a compatible PCM in liquid form are brought into contact with each other to allow the body of foam material to absorb the PCM liquid. One method, which is known as “float saturation”, involves placing the body of foam material into contact with the PCM liquid. Another method, which is knownas "top saturation", involves using a filling dispensing system to dispense a desired amount of the PCM in liquid form to the top of the body of foam material. In both cases, the open cells of the body of foam material become filled with the PCM. Optional additives (e.g., an antimicrobial agent, a viscosity modifier, a thermal conductivity modulator etc.) can be added to the PCM or to the body of foam material to provide different final properties. Finally, a plastic film of polyester or low-density polyethylene (LDPE) with variable thickness is used to protect and enclose the body of foam material, the PCM and the optional additives. The film is sealed to encapsulate the body of foam material and absorbed PCM / optional additives. It will be appreciated that a vacuum sealing process can be used to remove air from inside the container before it is sealed.

[0028] Fig. 3 is a top plan view of an exemplary device 100 for use in a thermally controlled package system according to the invention. And Fig. 4 is a section view of the exemplary device 100 shown in Fig. 3 taken along the lines 4-4, which shows a body of open-cell, low density, rigid (i.e., non-flexible), bio-based polymeric foam material 10 as shown in Fig. 1 that has absorbed a PCM 110 and is enclosed within a leakproof container 120, which in the illustrated embodiment is a pouch made of polymer film.

[0029] In one embodiment, the PCM comprises water. In other embodiments, the PCM comprises paraffin. Any paraffin not inconsistent with the objectives of the present invention may be used. In some embodiments, the paraffin comprises an n-alkane. In some embodiments, the paraffin comprises a C8 to C60 alkane. In some embodiments, the paraffin comprises a C8 to C20 alkane or a C20 to C40 or a C40 to C60 alkane. Non-limiting examples of paraffins suitable for use in some embodiments described herein include n-decane, n-dodecane, n-tridecane, n-tetradecane, n-pentadecane, n-hexadecane, n-heptadecane, n-octadecane, n-nonadecane, n-icosane, n-henicosane, n-docosane, n-tricosane, n-tetracosane, n-pentacosane, n-hexacosane, n-heptacosane, n-octacosane, n-nonacosane, n-triacontane, n-hentriacontane, n-dotriacontane, n-tritriacontane, and / or mixtures thereof.

[0030] In some embodiments, the PCM comprises a salt hydrate. Any salt hydrate not inconsistent with the objectives of the present invention may be used. Non-limiting examples of salt hydrates suitable for use in some embodiments described herein include KF 4H2O, Mn(NC>3)2-6H2O, CaChSF , CaBr2-6H2O,Li(NO3)-6H2O, Na2SO4-10H2O, Na2CO310H2O, Na2HPO4-12H2O, Zn(NO3)2-6H2O, Ca(NO3)2-3H2O, Na(NO3)2-6H2O, Zn(NO3)2-2H2O, FeCI3-2H2O, Co(NO3)2-6H2O, Ni(NO3)2-6H2O, MnCI2-4H2O, CH3COONa-3H2O, LiC2H3O2-2H2O, MgCI2-4H2O, NaOH H2O, Cd(NO3)24H2O, Cd(NO3)2-1 H20, Fe(NO3)2-6H2O, NaAI(SO4)2-12H2O, FeSO4-7H2O, Na3PO4-12H2O, Na2B4O710H2O, Na3PO4-12H2O, LiCH3COO-2H2O, and / or mixtures thereof.

[0031] In some embodiments, the PCM comprises a eutectic water-salt solution. Any eutectic water-salt solution not inconsistent with the objectives of the present invention may be used. Non-limiting examples of salt hydrates suitable for use in some embodiments described here include LiCI, CaCI2, MgCI2, AI(NO3)3, Li2SO4, NaCI, KCI, BaCI2, MgSO4, K2SO4, Na2SO4and / or mixtures thereof.

[0032] In some embodiments, the PCM comprises an alkyl ester of a fatty acid. Any alkyl ester not inconsistent with the objectives of the present invention may be used. For instance, in some embodiments, an alkyl ester comprises a methyl, ethyl, propyl, or butyl ester of a fatty acid described herein. In other embodiments, an alkyl ester comprises a C2 to C28 ester alkyl backbone or a C6 to C12 ester alkyl backbone. Further, in some embodiments, an oxidized fatty component described herein comprises a number of different alkyl esters of fatty acids. Non-limiting examples of alkyl esters of fatty acids suitable for use in some embodiments described herein include methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl palmitoleate, methyl oleate, methyl linoleate, methyl docosahexanoate, and methyl ecosapentanoate. In some embodiments, the corresponding ethyl, propyl, or butyl esters may also be used.

[0033] In some embodiments, the PCM comprises a fatty alcohol. Any fatty alcohol not inconsistent with the objectives of the present invention may be used. For instance, a fatty alcohol, in some embodiments, can have a C4 to C28 aliphatic hydrocarbon tail. Further, in some embodiments, the hydrocarbon tail is saturated. Alternatively, in other embodiments, the hydrocarbon tail is unsaturated. In some embodiments, the hydrocarbon tail can be branched or linear. Non-limiting examples of fatty alcohols suitable for use in some embodiments described herein include capryl alcohol, pelargonic alcohol, capric alcohol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, cetyl alcohol, heptadecyl alcohol, stearyl alcohol, nonadecyl alcohol, arachidyl alcohol, heneicosylalcohol, behenyl alcohol, lignoceryl alcohol, ceryl alcohol, and montanyl alcohol. In some embodiments, the PCM comprises mixtures of different fatty alcohols.

[0034] Further, in some embodiments, the PCM comprises a polyethylene glycol. Any polyethylene glycol not inconsistent with the objectives of the present invention may be used. In some embodiments, a PCM comprises a fatty sulfonate or phosphonate. Any fatty sulfonate or phosphonate not inconsistent with the objectives of the present invention may be used. The PCM comprises a C4 to C28 alkyl sulfonate or phosphonate in some embodiments. The PCM comprises a C4 to C28 alkenyl sulfonate or phosphonate in some embodiments.

[0035] In some embodiments, two or more different PCMs are used. Any combination of differing PCMs not inconsistent with the objectives of the present invention may be used. In some embodiments, for example, the PCM comprises one or more fatty acids and one or more fatty alcohols.

[0036] Preferred optional additives include an antimicrobial material. Any antimicrobial material not inconsistent with the objectives of the present invention may be used. In some embodiments, the antimicrobial material comprises a quarternary ammonium species. The quarternary ammonium species, in some embodiments, comprises a long alkyl chain, such as an alkyl chain having a C8 to C28 backbone. In some embodiments, the antimicrobial material comprises one or more from the family of Isothiazolinones such as methylisothiazolinone (Ml), methylchloroisothiazolinone (MCI), benzisothiazolinone (BIT), octylisothiazolione (OIT), and dichlorocthylisothiazolinone (DCOIT). In some embodiments, the antimicrobial material comprises an organic acid, such as lactic acid, acetic acid, or citric acid. In some embodiments, the antimicrobial material comprises one or more of benzalkonium chloride, benzethonium chloride, methylbenzethonium chloride, cetalkonium chloride, cetylpyridinium chloride, cetrimonium, cetrimide, dofanium chloride, tetraethylammonium bromide, didecyldimethylammonium chloride, and domiphen bromide. The antimicrobial material, in some embodiments, comprises an inorganic composition, including metals and / or metal salts. In some embodiments, for example, the antimicrobial material comprises metallic copper, zinc, or silver or a salt of copper, zinc, or silver. In other embodiments, the antimicrobial material comprises an organic composition, including natural and synthetic organic compositions. In some embodiments, the antimicrobial material comprises a p-lactam such as a penicillin or cephalosporin. In some embodiments, theantimicrobial material comprises a protein synthesis inhibitor such as neomycin. The amount of antimicrobial present is preferably within the range of from 0.1 to 1% by weight of the PCM, and more preferably from 0.01 to 0.1% by weight of the PCM.

[0037] In other embodiments, the optional additive comprises a thermal conductivity modulator. Suitable thermal conductivity modulators typically comprise carbon, including graphitic carbon. In some embodiments, the thermal conductivity modulator comprises carbon black and / or carbon nanoparticles. Carbon nanoparticles, in some embodiments, comprise carbon nanotubes and or fullerenes. In some embodiments, the thermal conductivity modulator comprises a graphitic matrix structure. In other embodiments, the thermal conductivity modulator comprises an ionic liquid. In some embodiments, the thermal conductivity modulator comprises a metal, including pure metals and alloys. Any metal not inconsistent with the objectives of the present invention may be used. In some embodiments, the metal comprises a transition metal, such as silver or copper. In some embodiments, the metal comprises an element from Group 13 or Group 14 of the periodic table. In some embodiments, the metal comprises aluminum. In some embodiments, the thermal conductivity modulator comprises a metallic filler, a metal matrix structure, a metal tube, a metal plate, metal shavings and / or metal hollow spheres. Further, in some embodiments, the thermal conductivity modulator comprises a metal oxide. Any metal oxide not inconsistent with the objectives of the present invention may be used. In some embodiments, the metal oxide comprises a transition metal oxide. In some embodiments, the metal oxide comprises alumina.

[0038] In addition, a viscosity modifier described herein can be present in any amount not inconsistent with the objectives of the present invention.

[0039] Viscosity modifiers comprise a thickening agent. Any viscosity modifier not inconsistent with the objectives of the present invention may be used. Preferred viscosity modifiers include polycarbohydrates - starches, agar, algin, xanthan gum, carboxymethyl cellulose (CMC), pectin, gelatin. In some embodiments, polyethylene glycol, polyvinyl alcohol, and polyacrylates are used as viscosity modifiers. In some embodiments, attapulgite, bentonite, and montmorillonite clays are used.

[0040] Any combination of additives described herein not inconsistent with the objectives of the present invention may be used. For instance, in some embodiments, the additives include a combination of one or more thermalconductivity modulators, one or more antimicrobial materials, and / or one or more materials that contain or act as fire retardants.

[0041] Preferably the body of foam material, the PCM, and any optional additives are enclosed within a container. In a preferred method the body of foam material, the PCM and any optional additives present are sealingly enclosed within a lightweight, non-reactive polymeric film. The polymeric film preferably comprises polyethylene - low-density polyethylene, medium-density polyethylene, high-density polyethylene, or linear low-density polyethylene, polypropylene, polyester, nylon, polyvinyl chloride, and a variety of bioplastics and biodegradable plastics such as starch, polylactic acid (PLA), polybutylene succinate (PBS), polybutylene adipate terephthalate (PBAT) and / or polyhydroxybutyrate (PHB).

[0042] Fig. 5 is a top view of an exemplary shipping container 130 before it has been sealed The exemplary shipping container 130 shown in Fig. 5 includes a paperboard box 140, insulation 150 and a device 100 as shown in Fig. 3. In the illustrated embodiment, insulation is placed in contact with all inner sides of the paperboard box 140 and a device 100 as shown in Fig. 3 is placed on the bottom layer of insulation. The remaining space above the device 100 provides a cavity for receiving a temperature-controlled product to be shipped. In the illustrated embodiment, a second device 100 would be placed atop the temperature-controlled product to be shipped, then the top layer of insulation would be folded onto the top of the second device 100 and the flaps of the paperboard box 140 would be closed to seal the shipping container 130.

[0043] Fig. 6 is a section view of the exemplary shipping container 130 shown in Fig. 5 taken along the lines 6-6 after it has been filled with a temperature-controlled product to be shipped 160, another device 100 as shown in Fig. 3, and sealed. It will be appreciated that any number of devices 100 can be used in a shipping container 130, including one, two, three, four, five, six and more than six, and that the selection of the number of devices 100 to be used will be based, at least in part, on the shape and / or properties of the temperature-controlled product 160 to be shipped. It will also be appreciated that the dimensions of the shipping container 130 and the devices 100 contained therein will be determined based on the shape and size of the temperature-controlled product 160 to be shipped.

[0044] In some applications, a paperboard box is not used, nor is insulation. The shipping container can simply comprise a polymeric container that contains one ormore devices according to the invention and a product to be shipped. It will also be appreciated that the device according to the invention can have a shape other than a block (e.g., can be specially formed to have contours compatible with the product to be shipped).EXAMPLES

[0045] The following examples set forth in detail certain illustrative embodiments of the invention, these being indicative of a few of the various ways in which the principles of the present invention may be employed.Example 1

[0046] A 10 x 8 x 1 inch bio-based foam (OASIS® Renewal® Floral Foam) was “float saturated” in water as a phase change material to about 95% w / v of the dimensions of the body of foam material. A quaternary ammonium chloride compound was added as an antimicrobial in an amount between 0.001 to 0.01% v / v of the PCM. Finally, the foam, PCM and additive were enclosed in a polyester plastic film, which was heat-sealed.Example 2

[0047] An 8 x 8 x 1 inch bio-based foam (OASIS® Renewal® Floral Foam) was “float saturated” using a water-salt (sodium chloride NaCI) phase change material to within 80 to 88% w / v of foam dimensions. A quaternary ammonium chloride compound was added as an antimicrobial in the amount of between 0.001 to 0.01% v / v of the PCM. Finally, the foam, PCM and additive were enclosed in a polyester plastic film, which was heat-sealed.Example 3

[0048] A 4.5 x 4 x 1 inch bio-based foam (OASIS® Renewal® Floral Foam) was “top saturated” using tetradecane, a hydrocarbon base phase change material to within 80 to 88% w / v of foam dimensions. The foam and PCM were enclosed in a polyester plastic film, which was heat-sealed to form a leakproof container.Example 4

[0049] A 4.5 x 4 x 1 inch bio-based (OASIS® Renewal® Floral Foam) foam was "float saturated” using methyl laurate, an ester-base phase change material to within 80 to 88% w / v of foam dimensions. The foam and PCM were enclosed in a polyester plastic film, which was heat-sealed to form a leakproof container.Example 5

[0050] 9.5 x 9.5 x 1 inch devices were prepared according to Example 1 and then tested for use as a temperature control devices in an insulated shipping container such as shown in Fig. 5, which contained a payload box as a temperature-controlled product. The test conditions / results / data are reported in Table 1 below:Table 1

[0051] Fig. 7 is a graph showing ambient room temperature (RT) outside the shipping container and the inside temperature measured at the top of the payload box contained within a shipping container, respectively, as a function of time. The data shows that the temperature at the top of the payload box remained below the freezing temperature of water for 36 hours and did not rise to 50° F until 72 hours despite the shipping container being exposed to ambient temperatures greater than 70° F (and as high as 95° F) over that period of time.Example 6

[0052] 8.5 x 5.5 x 0.625 inch devices were prepared according to Example 1 and then tested for use as a temperature control devices in an insulated shipping container such as shown in Fig. 5, which contained a payload box as a temperature-controlled product. The test conditions / results / data are reported in Table 2 below:Table 2

[0053] Fig. 8 is a graph showing ambient room temperature (RT) outside the shipping container and the inside temperature measured at the top of the payload box contained within a shipping container, respectively, as a function of time. The data shows that the temperature at the top of the payload box initially dropped to below the freezing temperature of water and then stayed slightly above the freezing temperature of water for 36 hours and did not rise to 50° F until about 40 hours despite the shipping container being exposed to ambient temperatures greater than 70° F (and as high as 95° F) over that period of time.Example 7

[0054] Table 3 shows the composition of the PCM, whether 125 ml of the PCM was absorbed in the bio-based foam (OASIS® Renewal® Floral Foam), and theamount of time required for a piece of the foam having a 2 in square diameter and a 1 inch thickness to absorb the PCM.Table 3

[0055] Additional advantages and modifications will readily occur to those skilled in the art. Therefore, the invention in its broader aspects is not limited to the specific details and illustrative examples shown and described herein. Accordingly, various modifications may be made without departing from the spirit or scope of the general inventive concept as defined by the appended claims and their equivalents.

Claims

What is claimed is:Claim 1 (original): A device for use in a thermally controlled package system, the device comprising:a body of open cell, low-density, rigid, bio-based polymeric foam material; and a phase change material absorbed in the body of foam material; wherein the body of foam material is shape-stable upon absorption of the phase change material, andwherein the body of foam material and the phase change material absorbed in the body of foam material are enclosed within a leakproof container.Claim 2 (original): The device according to claim 1, wherein the leakproof container is formed of polymeric film.Claim 3 (original): The device according to claim 1, wherein the body of foam material comprises at least 80% by weight of one or more polymers that are of plant origin.Claim 4 (original): The device according to claim 1, wherein the body of foam material is formed of one or more selected from the group consisting of tannin resins, lignin resins, cardanol resins, furfuryl alcohol resins, and bio-based phenol resins.Claim 5 (original): The device according to claim 1, wherein the body of foam material is formed of two or more selected from the group consisting of tannin resins, lignin resins, cardanol resins, furfuryl alcohol resins, and bio-based phenol resins.Claim 6 (original): The device according to claim 1, wherein the body of foam material comprises a tannin resin.Claim 7 (original): The device according to claim 1, wherein the body of foam material comprises a lignin resin.Claim 8 (original): The device according to claim 1, wherein the body of foam material comprises a cardanol resin.Claim 9 (original): The device according to claim 1, wherein the body of foam material comprises a furfuryl alcohol resin.Claim 10 (original): The device according to claim 1, wherein the body of foam material comprises a bio-based phenol resin.Claim 11 (original): The device according to claim 1 , wherein the body of foam material comprises a polyurethane foam made from bio-based polyols.Claim 12 (original): The device according to claim 11 , wherein the polyols are made from one or more selected from the group consisting of soybean oil, castor oil, palm oil, cardanol, glycerol, and other hydroxyl-containing plant-based materials.Claim 13 (original): The device according to claim 1, wherein the body of foam comprises a starch foam, a polylactic acid foam (PLA), a polyhydroxyalkanoate foam, a cellulose foam, a cellulose acetate foam, a cellulose ester foam, a cellulose fiber-based foam, a wood fiber foam, a cellulose nanofiber foam (CNF), a microfibrillated cellulose foam (MFC), a lignocellulosic foam, a chitin and / or chitosan based foam, a bio-based polybutylene succinate (PBS) foam, an alginate based foam, or a cellulose acetate foam.Claim 14 (original): The device according to claim 4, wherein the body of foam material has a 90% to 99% open cell content.Claim 15 (original): The device according to claim 4, wherein the body of foam material has a 95% to 99% open cell content.Claim 16 (original): The device according to claim 4, wherein the body of foam material has a density of from about 1.0 to about 2.0 lb / ft3.Claim 17 (original): The device according to claim 4, wherein the body of foam material has a density of from about 1.0 to about 1.5 lb / ft3.Claim 18 (original): The device according to claim 4, wherein the body of foam material has a compression strength of from about 6.0 to about 18 lbf / in2.Claim 19 (original): The device according to claim 4, wherein the body of foam material has a compression strength of from about 10 to about 15 lbf / in2.Claim 20 (original): The device according to claim 4, wherein the body of foam material has macropores having a diameter of from about 50 to about 500 microns, and micropores having a diameter of from about 0.5 to about 50 microns.Claim 21 (original): The device according to claim 4, wherein the body of foam material has a 90% to 99% open cell content, wherein the body of foam material has a density of from about 1.0 to about 2.0 lb / ft3, wherein the body of foam material has a compression strength of from about 6.0 to about 18 lbf / in2, and wherein the body of foam material has macropores having a diameter of from about 50 to about 500 microns, and wherein the body of foam material has micropores having a diameter of from about 0.5 to about 50 microns.Claim 22 (original): The device according to claim 1 , wherein the phase change material absorbed in the body of foam material comprises one or more selected from the group consisting of water, paraffin waxes, water-salt eutectic solutions, water-eutectic solutions, salt hydrates, fatty acids, alkyl esters of fatty acids, fatty alcohols, fatty sulfonates or phosphonates and combinations thereof.Claim 23 (original): The device according to claim 1 , wherein the phase change material absorbed in the body of foam material comprises one or more selected from the group consisting of water, paraffin waxes, water-salt eutectic solutions, water-eutectic solutions, salt hydrates, fatty acids, alkyl esters of fatty acids, fatty alcohols, fatty sulfonates or phosphonates and combinations thereof.Claim 24 (original): The device according to claim 1 , wherein the device further comprises one or more additives selected from the group consisting of antimicrobials, viscosity modifiers, and thermal conductivity modulators present in the foam and / or the phase change material.

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